CN101300286B - Optical device and achromatic lens - Google Patents

Optical device and achromatic lens Download PDF

Info

Publication number
CN101300286B
CN101300286B CN2006800409604A CN200680040960A CN101300286B CN 101300286 B CN101300286 B CN 101300286B CN 2006800409604 A CN2006800409604 A CN 2006800409604A CN 200680040960 A CN200680040960 A CN 200680040960A CN 101300286 B CN101300286 B CN 101300286B
Authority
CN
China
Prior art keywords
carbonatoms
formula
structural unit
phenyl
polymkeric substance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2006800409604A
Other languages
Chinese (zh)
Other versions
CN101300286A (en
Inventor
畠中邦夫
今中嘉彦
门利昌则
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Ltd
Original Assignee
Teijin Chemicals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Teijin Chemicals Ltd filed Critical Teijin Chemicals Ltd
Publication of CN101300286A publication Critical patent/CN101300286A/en
Application granted granted Critical
Publication of CN101300286B publication Critical patent/CN101300286B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/10—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0025—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration
    • G02B27/0037—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration with diffracting elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/42—Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect
    • G02B27/4205—Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect having a diffractive optical element [DOE] contributing to image formation, e.g. whereby modulation transfer function MTF or optical aberrations are relevant
    • G02B27/4211—Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect having a diffractive optical element [DOE] contributing to image formation, e.g. whereby modulation transfer function MTF or optical aberrations are relevant correcting chromatic aberrations
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/42—Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect
    • G02B27/4272—Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect having plural diffractive elements positioned sequentially along the optical path

Abstract

The invention relates to an optical device which is characterized by being used for correction of chromatic aberration, characterized in that the optical device is composed of a polymer having a structural unit derived from a specific dihydroxy compound typified by 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (bisphenol AF), whose refractive index nD and Abbe number vD satisfy the following relation (I); and the invention is also used for the correction of chromatic aberration: nD+0.0076*vD is less than or equal to 1.78 (I).

Description

Optical element and achromatic lens
Technical field
The present invention relates to a kind of optical element and achromatic lens.
Background technology
The short-wavelength light index of refraction in lens of known optical lens (convex lens) is bigger than the long wavelength light index of refraction in lens, that is, show upward aberration of axle, and produce bleeding (aberration).Because aberration becomes problem in the use, therefore, optical lens usually and the achromatic element is made up and conduct is used lens combination or the cascade type lens that aberration carried out revisal.
As the achromatic element, bring into use concave mirror a long time ago, but the use of Fresnel lens in recent years very noticeable (please refer to the flat 9-127321 of TOHKEMY number, the flat 9-127322 of TOHKEMY number, TOHKEMY 2004-78166 number and TOHKEMY 2005-107298 number).
For the revisal aberration, a plurality of elements are constituted lens combination, these a plurality of elements are made of the different material that the Abbe number as the index of weighing the aberration degree differs greatly.As lens material, adopt glass all the time.The specific refractory power of glass is about 1.46～1.92, Abbe number is about 25～80, can select optical characteristics in the scope extremely widely, therefore, being used for the degree of freedom height of design of the lens combination of revisal aberration, is the material that helps bringing into play multiple lens peculiarity.
When aforesaid lens combination was applicable to camera or pick up camera etc., requiring lens combination was small-sized, lightweight.Particularly, telephoto lens system that lens diameter is big or super telephoto lens system all are heavy, thick, long, big all the time, when it being installed in the camera bad operation when using, miss camera lens sometimes, therefore, require the lightweight of lens combination and the shorteningization of lens combination total length.For this reason, when being necessary to re-recognize lens material, the focal length behind the shortening achromatic.
From above viewpoint,, wait in expectation and to replace glass by enough plastic materials as lens material.
At present, as the representative materials of plastic lens, can enumerate polymethylmethacrylate (PMMA) and polycarbonate.Wherein, PMMA is except having advantages such as the transparency and hardness height, excellent in te pins of durability, and its Abbe number is 57 high value, and therefore, the aspect little from aberration in most cases is used.
As the plastic lens material of the achromatic that is used for the PMMA lens, adopt by 2 the polycarbonate (PC (BIS-A)) that two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) of 2-are made usually.The Abbe number of PC (BIS-A) is 32, since very big with the difference of the Abbe number 57 of PMMA, therefore, possessed the important document that is used for achromatic.But even pass through the use of PC (BIS-A), the focal length behind the achromatic does not reach the well-content level of making us yet.
But,, think that the specific refractory power of lens material is high more good more in the past from the light-weighted viewpoint of lens.That is, when specific refractory power is low,, the curvature of lens must be diminished, therefore, have to the whole thickening of lens is run counter to light-weighted requirement like this in order to obtain desirable effect.
Known in plastic optics material in the past, certain relation is arranged between specific refractory power and the Abbe number.With Fig. 1 optics general in the known document specific refractory power of plastic material and the relation of Abbe number are shown.As shown in Figure 1, the specific refractory power with plastic material is the low more tendency of high Abbe number more, marks and draws the set of the point of both sides relation in each material, concentrates in the extremely narrow zone.The effort that the improvement as the plastic material of optical element is in the past done, be primarily aimed at the exploitation that surmounts material this zone, the demonstration high refractive index and (please refer to daily use chemicals association monthly magazine, 40 (8), 27 (1987)) and daily use chemicals associations monthly magazine 47 (2), 8 (1994)).
But, to as the achromatic in the lens combination with suitable and can constitute the achromatic element of the lens combination that the focal length behind the achromatic shortens, also do not know to adopt on earth which type of material suitable.
In addition, polycarbonate material is widely known by the people as having the transparency and stable on heating material all the time, has carried out many improved researchs.But great majority are in order to improve mechanical characteristics (with reference to the flat 6-145333 of TOHKEMY number and the flat 6-200005 of TOHKEMY number) as engineering plastics or the research of carrying out in order to be applicable to special purpose (the flat 5-294029 of TOHKEMY number).Research as optical applications, the photoreceptor that duplicates as optical fiber, photograph or the recording layer of CD are used etc., nearly all are only to be the improvement (with reference to the flat 6-347650 of TOHKEMY number, the flat 3-61911 of TOHKEMY number, the flat 6-282094 of TOHKEMY number and the clear 64-31825 of TOHKEMY number) of the mechanical characteristics in the field of object with the single wavelength.Only in the clear 62-18501 of TOHKEMY number, inquired into the improvement when polycarbonate material is applicable to lens, but carry out this moment is to be the research of the material of purpose with the thermotolerance and the surface hardness that improve lens, and only discloses the convex lens that is formed by this material in an embodiment.
Summary of the invention
The present invention finishes in view of the above fact, and its purpose is, optical element that a kind of achromatic that is suitable as lens combination or cascade type lens uses and the achromatic lens that has used this optical element are provided.
Optical element of the present invention, for example can make forms such as concave mirror, Fresnel lens, diffraction grating, can be made up with other optical element (for example convex lens, Fresnel lens, diffraction grating etc.) and be used for the formation of the achromatic lens of achromatic lens system or cascade type.
Above-mentioned previous purpose of the present invention realizes that in the following manner promptly, a kind of optical element is characterized in that, by the structural unit that has with following general formula (i) expression, and refractive index n DWith Abbe number ν DThe relation polymkeric substance that satisfies following formula (I) constitute, and be used for achromatic.
n D+0.0076×ν D≤1.78 (I)
Figure S2006800409604D00031
(in the formula (i), a plurality of R 1Being independently selected from respectively by carbonatoms is that 1～10 alkyl, carbonatoms are that 1～10 alkoxyl group, carbonatoms are that 6～20 cycloalkyl, carbonatoms are that 6～20 cycloalkyloxy, carbonatoms are 6～10 aryl, carbonatoms is that 7～20 aralkyl, carbonatoms are that 6～10 aryloxy and carbonatoms are the group's that forms of 7～20 aralkoxy any monovalent organic radical group or halogen atom, and part or all of the hydrogen atom in the described any monovalent organic radical group can be replaced by halogen atom; P and q represent 0～4 integer respectively independently; A is singly-bound or is selected from the divalent group in the following formula (i-1)～(i-4).Wherein, when A was the divalent group of singly-bound or non-contain fluorine atoms, P and q can not be 0 simultaneously, the R that exists in the formula (i) 1At least one be any monovalent organic radical group or fluorine atom, part or all of the hydrogen atom of described any monovalent organic radical group replaced by fluorine atom.)
Figure S2006800409604D00032
(in the formula (i-1), a plurality of R 2Part or all carbonatoms that can be replaced by halogen atom of representing hydrogen atom or halogen atom or expression hydrogen atom respectively independently is 1～10 alkyl.)
Figure S2006800409604D00041
(in the formula (i-2)～(i-4), a plurality of R 3, R 4And R 5Part or all carbonatoms that can be replaced by halogen atom of representing hydrogen atom or halogen atom or expression hydrogen atom respectively independently is 1～4 alkyl, and the r in the formula (i-3) is 4～11 integer.)
An above-mentioned back purpose of the present invention realizes that in the following manner promptly, a kind of achromatic lens is characterized in that, by Abbe number ν DBe 50～60, refractive index n DBe that the optical element that constitutes of 1.48～1.55 material and above-mentioned optical element constitute.
Adopt the achromatic lens amount of the present invention of optical element of the present invention light, and the focal length behind its achromatic is short, can be suitable in the telephoto lens system or super telephoto lens system of the camera of analog or digital or pick up camera etc.
Description of drawings
The graphic representation that Fig. 1 concerned between the specific refractory power of known plastic lens material and the Abbe number for expression in the past.Illustrated by the flat 1-66234 of TOHKEMY number, the flat 5-294671 of TOHKEMY number, the flat 6-25398 of TOHKEMY number, the flat 6-228296 of TOHKEMY number, the flat 6-248063 of TOHKEMY number, the flat 6-263861 of TOHKEMY number, the flat 11-349676 of TOHKEMY number, TOHKEMY 2000-47001 number, TOHKEMY 2000-63506 number, TOHKEMY 2000-95933 number, TOHKEMY 2000-136241 number, TOHKEMY 2000-136242 number, TOHKEMY 2000-230044 number, TOHKEMY 2000-302860 number, TOHKEMY 2001-11165 number, TOHKEMY 2001-11166 number, TOHKEMY 2001-11168 number, TOHKEMY 2001-11169 number, TOHKEMY 2002-90501 number, TOHKEMY 2002-201277 number, TOHKEMY 2002-212275 number, TOHKEMY 2002-265585 number, TOHKEMY 2002-226570 number, TOHKEMY 2002-293911 number, TOHKEMY 2002-293912 number, TOHKEMY 2002-338678 number, TOHKEMY 2002-371179 number, TOHKEMY 2003-48974 number, TOHKEMY 2003-55543 number, TOHKEMY 2003-73468 number, TOHKEMY 2003-90901 number, TOHKEMY 2003-160659 number, TOHKEMY 2003-160660 number, TOHKEMY 2004-75799 number, TOHKEMY 2004-10801 number, TOHKEMY 2005-42032 number, TOHKEMY 2005-77963 number, the embodiment collection of the clear 64-31825 of TOHKEMY number and the clear 62-18501 communique of TOHKEMY.
Fig. 2 is the synoptic diagram of the preferred embodiment of the achromatic lens system of employing optical element of the present invention.
Fig. 3 is the synoptic diagram of the preferred embodiment of achromatic lens of the present invention.
Fig. 4 is the synoptic diagram of the preferred embodiment of achromatic lens of the present invention.
Embodiment
Optical element of the present invention is by the polymkeric substance formation that has with the structural unit of above-mentioned formula (i) expression.
As with the halogen atom in the structural unit of following formula (i) expression, can enumerate fluorine atom, chlorine atom, bromine atoms and iodine atom, wherein, be preferably fluorine atom.
In structural unit with following formula (i) expression, when A is singly-bound, R 1Be preferably fluorine atom.
With following formula (i) expression structural unit in, when A for following formula (i-1) expression divalent group the time, R 2Be preferably hydrogen atom, fluorine atom, methyl, difluoromethyl, carbonatoms and be 1～10 perfluoroalkyl, phenyl, fluoro phenyl or perfluorophenyl.As above-mentioned carbonatoms is 1～10 perfluoro-methyl, for example can enumerate trifluoromethyl, perfluor n-propyl, perfluor n-nonyl etc., preferred especially trifluoromethyl.As two R 2When being selected from any group in hydrogen atom, methyl and the phenyl, at least one among preferred p and the q is not 0, and R simultaneously 1In at least one be fluorine atom or trifluoromethyl.
In structural unit with following formula (i) expression, when A for the divalent group of following formula (i-2) expression the time, preferred R 3Be that carbonatoms is 1～4 perfluoroalkyl, be preferably trifluoromethyl especially.When A is that preferred p and q are 0 simultaneously when using the divalent group of following formula (i-2) expression.
In structural unit with following formula (i) expression, when A for the divalent group of following formula (i-3) expression the time, preferred R 4Be hydrogen atom or fluorine atom, preferred r is 4,5 or 11.As two R 4When being hydrogen atom simultaneously, at least one among preferred p and the q be not for being 0, and R 1In at least one be fluorine atom.
In structural unit with following formula (i) expression, when A for the divalent group of following formula (i-4) expression the time, preferred R 5Be hydrogen atom, at least one among preferred p and the q be not for being 0, and R 1In at least one be 1～4 perfluoroalkyl for fluorine atom or carbonatoms.At this, be 1～4 perfluoroalkyl as carbonatoms, be preferably trifluoromethyl especially.
In structural unit with following formula (i) expression, the weight ratio F of preferred fluorine content MBe 0.22～0.63, more preferably 0.25～0.55.At this said fluorine content weight ratio F M, be meant the value of the weight of the fluorine atom that contains in the structural unit (i) divided by the weight of structural unit (i).
Has polymkeric substance with the structural unit of following formula (i) expression, can be by using interfacial polymerization, solution polymerization process or melt phase polycondensation, make dihydroxy compound, that is, make by the compound of following formula (i ') expression and carbonic ether presoma and react and obtain corresponding to desired structural unit.At this moment, with the structural unit of following formula (i) expression by compound deriving with following formula (i ') expression.
Figure S2006800409604D00061
(formula (i ') in, R 1, p, q and A definition identical with the definition in the following formula (i).)
Below, about the object lesson of structural unit, be illustrated according to the object lesson of the dihydroxy compound of this structural unit of deriving (i ') with following formula (i) expression.For a person skilled in the art, can both easily understand when specific dihydroxy compound (i ') during with the reaction of carbonic ether presoma, can be obtained having the polymkeric substance corresponding to the structural unit (i) of the structure of this oxy-compound.
As the A in the following formula of deriving (i) is the dihydroxy compound (i ') of single bonded structural unit, for example, can enumerate octafluoro-4,4 '-bis-phenol, 3,3 '-two fluoro-4,4 '-bis-phenol, 3,3 ', 5,5 ' ,-tetrafluoro-4,4 '-bis-phenol, 2,2 ', 5,5 ' ,-tetrafluoro-4,4 '-bis-phenol etc.
As the A in the following formula of deriving (i) is the dihydroxy compound (i ') of the structural unit of formula (i-1), for example, can enumerate 1, two (the 3-fluoro-4-hydroxy phenyl) methane of 1-, 1,1-two (3,5-two fluoro-4-hydroxy phenyls) methane, 1, two (the 4-hydroxy phenyls)-2 of 1-, 2-C2H4F2 C2H4F2,1, two (the 4-hydroxy phenyls)-2 of 1-, 2, the 2-Halothane, 2, two (the 3-fluoro-4-hydroxy phenyl) propane of 2-, 2,2-two (3,5-two fluoro-4-hydroxy phenyls) propane, 2, two (4-hydroxyl-3-trifluoromethyl) propane of 2-, 2, two (the 4-hydroxy phenyls)-1 of 2-, 1,1-trifluoro propane, 2, two (3,5-dimethyl-4-hydroxy phenyl)-1 of 2-, 1,1-trifluoro propane, 2, two (the 4-hydroxy phenyls)-1,1 of 2-, 1,3, the 3-pentafluoropropane, 2, two (the 4-hydroxy phenyls)-1 of 2-, 1,1,3,3,3-HFC-236fa (those skilled in the art are called " bisphenol AF "), 2, two (the 4-hydroxy-3-methyl phenyl)-1,1,1 of 2-, 3,3, the 3-HFC-236fa, 2,2-two (3,5-dimethyl-4-hydroxy phenyl)-1,1,1,3,3, the 3-HFC-236fa, 2, two (the 3-fluoro-4-hydroxy phenyls)-1,1 of 2-, 1,3,3, the 3-HFC-236fa, 2,2-two (3,5-two fluoro-4-hydroxy phenyls)-1,1,1,3,3, the 3-HFC-236fa, 2, two (the 4-hydroxyls-2 of 2-, 3,5,6-tetrafluoro phenyl)-1,1,1,3,3, the 3-HFC-236fa, 2, two (the 4-hydroxyls-3-phenyl)-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 2, two [4-hydroxyl-3-(2-propyl group) phenyl]-1,1 of 2-, 1,3,3, the 3-HFC-236fa, 1, two (4-hydroxy phenyl) perfluorinated butanes of 1-, 1, two (4-hydroxy phenyl) PFO of 1-, 1, two (4-hydroxy phenyl) perfluoro decanes of 1-, 1, two (4-the hydroxy phenyl)-1-phenyl-2 of 1-, 2, the 2-Halothane, 1, two (4-the hydroxy phenyl)-1-(2,3 of 1-, 4,5,6-hexafluoro phenyl) methane, 1, two (4-the hydroxy phenyl)-1-phenyl-fluoride methane of 1-, 1, two (3-fluoro-4-the hydroxy phenyl)-1-phenylmethanes of 1-, 1, two (4-hydroxyl-3,5-the difluorophenyl)-1-phenylmethanes of 1-, two (3-fluoro-4-hydroxy phenyl) ditan, two (4-hydroxyl-3,5-difluorophenyl) ditan, 1, two (3-fluoro-4-hydroxy phenyl)-1-(4-fluorophenyl) ethane of 1-, 1, two (4-hydroxyl-3,5-difluorophenyl)-1-(4-fluorophenyl) ethane of 1-, 1, two (4-hydroxy phenyl)-1-(4-fluorophenyl) ethane of 1-etc.
As the A in the following formula of deriving (i) is the dihydroxy compound (i ') of the structural unit of formula (i-2), can enumerate α, α '-two (4-hydroxy phenyl)-two (1,1,1,3,3,3-hexafluoro sec.-propyl) benzene, α, α '-two (4-hydroxy phenyl)-to two (1,1,1,3,3,3-hexafluoro sec.-propyl) benzene etc.
As the A in the following formula of deriving (i) is the dihydroxy compound (i ') of the structural unit of formula (i-3), for example, can enumerate 1, two (the 3-fluoro-4-hydroxy phenyl) hexanaphthenes, 1 of 1-, two (4-hydroxy phenyl) Decafluorocyclopentanes, 1 of 1-, two (4-hydroxy phenyl) the perfluor hexanaphthenes, 1 of 1-, two (4-hydroxy phenyl) perfluor cyclododecanes of 1-etc.
As the A in the following formula of deriving (i) is the dihydroxy compound (i ') of the structural unit of formula (i-4), for example, can enumerate 9, two (the 3-fluoro-4-hydroxy phenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-trifluoromethyl) fluorenes of 9-etc.
Wherein, in order to realize with the fluorine content weight ratio F in the structural unit of following formula (i) expression WPreferred value, as employed dihydroxy compound (i '), preferably the fluorine content weight ratio F from this dihydroxy compound deutero-structural unit WBe 0.22～0.63, more preferably 0.25～0.55.Enumerate the preferred object lesson of the dihydroxy compound selected according to this viewpoint (i ') below.In addition, in following illustration, the fluorine content weight ratio F of the numeric representation in [] from each preferred dihydroxy compound (i ') deutero-structural unit (i) W
As A is single bonded dihydroxy compound, for example, can enumerate octafluoro-4,4 '-bis-phenol [0.43], 3,3 ', 5,5 '-tetrafluoro-4,4 '-bis-phenol [0.27] and 2,2 ', 5,5 '-tetrafluoro-4,4 '-bis-phenol [0.27];
As A is the dihydroxy compound of formula (i-1), for example, can enumerate 1, two (3, the 5-two fluoro-4-hydroxy phenyls) methane [0.25] of 1-, 2,2-two (3,5-two fluoro-4-hydroxy phenyls) propane [0.23], 2, two (4-hydroxyl-3-trifluoromethyl) propane [0.29] of 2-, 2, two (the 4-hydroxy phenyls)-1 of 2-, 1,1,3,3-pentafluoropropane [0.28], bisphenol AF [0.31], 2, two (the 4-hydroxy-3-methyl phenyl)-1,1 of 2-, 1,3,3,3-HFC-236fa [0.29], 2, two (3,5-dimethyl-4-hydroxy phenyl)-1 of 2-, 1,1,3,3,3-HFC-236fa [0.27], 2, two (the 3-fluoro-4-hydroxy phenyls)-1 of 2-, 1,1,3,3,3-HFC-236fa [0.38], 2,2-two (3,5-two fluoro-4-hydroxy phenyls)-1,1,1,3,3,3-HFC-236fa [0.44], 2,2-two (4-hydroxyl-2,3,5,6-tetrafluoro phenyl)-1,1,1,3,3,3-HFC-236fa [0.53], 2, two (the 4-hydroxyls-3-phenyl)-1,1,1 of 2-, 3,3,3-HFC-236fa [0.22], 2, two (4-hydroxyl-3-(2-propyl group) phenyl)-1 of 2-, 1,1,3,3,3-HFC-236fa [0.26], 1, two (4-the hydroxy phenyl)-perfluorinated butanes [0.37] of 1-, 1, two (4-the hydroxy phenyl)-PFO [0.51] of 1-, 1, two (4-the hydroxy phenyl)-perfluoro decanes [0.54] of 1-, 1, two (4-the hydroxy phenyl)-1-(2,3,4 of 1-, 5, the 6-pentafluorophenyl group) methane [0.24] and 1, two (4-hydroxyl-3,5-difluorophenyl)-1-(4-fluorophenyl) ethane [0.23] of 1-;
As A is the dihydroxy compound of formula (i-2), for example, can enumerate α, α '-two (4-hydroxy phenyl)-two (1,1,1,3,3,3-hexafluoro sec.-propyl) benzene [0.39] and α, α '-two (4-hydroxy phenyl)-to two (1,1,1,3,3,3-hexafluoro sec.-propyl) benzene [0.39];
As A is the dihydroxy compound of formula (i-3), for example, can enumerate 1, two (4-hydroxy phenyl) Decafluorocyclopentanes [0.35], 1 of 1-, two (4-hydroxy phenyl) the perfluor hexanaphthenes [0.39] and 1 of 1-, two (4-hydroxy phenyl) the perfluor cyclododecanes [0.54] of 1-;
As A is the dihydroxy compound of formula (i-4), for example, can enumerate 9, two (4-hydroxyl-3-trifluoromethyl) fluorenes [0.22] of 9-.
From improving the fluorine content weight ratio F the structural unit easily WViewpoint consider that the fluorine atom of preferably using the structural unit of following formula (i) expression to have is the fluorine atom from perfluoroalkyl.
From this viewpoint, the A of structural unit that preferably uses following formula (i) expression is for the following formula (i-1) or (i-2) divalent group of expression, when A for the divalent group of following formula (i-1) expression the time, the R that preferred structure unit (i) has 2In at least one be the perfluoroalkyl of carbonatoms 1～10, in addition, when A for following formula (i-2) expression divalent group the time, the R that preferred structure unit (i) has 3In at least one be the perfluoroalkyl of carbonatoms 1～4.
As the preferred dihydroxy compound of structural unit (i) that is used to derive so (i '), when A is the dihydroxy compound of following formula (i-1), can enumerate bisphenol AF, 2, two (4-hydroxyl-3 aminomethyl phenyls)-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 2, two (3,5-dimethyl-4-hydroxy phenyl)-1,1 of 2-, 1,3,3, the 3-HFC-236fa, 2, two (the 3-fluoro-4-hydroxy phenyls)-1,1,1,3 of 2-, 3, the 3-HFC-236fa, 2, two (3,5-two fluoro-4-hydroxy phenyls)-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 2,2-two (4-hydroxyl-2,3,5,6-tetrafluoro phenyl)-1,1,1,3,3, the 3-HFC-236fa, 2, two (the 4-hydroxyls-3-phenyl)-1,1 of 2-, 1,3,3, the 3-HFC-236fa, 2, two (4-hydroxyl-3-(2-propyl group) phenyl)-1,1,1 of 2-, 3,3, the 3-HFC-236fa, 1, two (4-the hydroxy phenyl)-perfluorinated butanes of 1-, 1, two (4-the hydroxy phenyl)-PFO and 1 of 1-, two (4-the hydroxy phenyl)-perfluoro decanes of 1-; When A is the dihydroxy compound of following formula (i-2), can enumerate α, α '-two (4-hydroxy phenyl)-two (1,1,1,3,3,3-hexafluoro sec.-propyl) benzene and α, α '-two (4-hydroxy phenyl)-to two (1,1,1,3,3,3-hexafluoro sec.-propyl) benzene.
Wherein, be easy to get calmly and the viewpoint of processing ease is considered, preferred especially bisphenol AF.
These dihydroxy compound (i ') both can use separately, also can be used in combination.
The polymkeric substance that uses among the present invention can also have other structural unit except the structural unit with following formula (i) expression.Summation amount with respect to the structural unit of representing with following formula (i) and other structural units, the content of the structural unit that contains in the polymkeric substance (i) is preferably 50 moles more than the %, more preferably 75 moles more than the %, more preferably 75～99 moles of % are preferably 75～95 moles of % especially.
Can be included in other structural units in the polymkeric substance of the present invention with structural unit with following formula (i) expression, be preferably from the dihydroxy compound deutero-structural unit beyond the compound of following formula (i ') expression, as its concrete example, can enumerate (ii) or the structural unit of (iii) representing with following formula:
Figure S2006800409604D00101
(formula (ii) in, a plurality of R 6Being independently selected from respectively by carbonatoms is that 1～10 alkyl, carbonatoms are that 1～10 alkoxyl group, carbonatoms are that 6～20 cycloalkyl, carbonatoms are that 6～20 cycloalkyloxy, carbonatoms are 6～10 aryl, carbonatoms is that 7～20 aralkyl, carbonatoms are that 6～10 aryloxy and carbonatoms are any monovalent organic radical group among the group that forms of 7～20 aralkoxy or the halogen atom beyond the fluorine atom, and part or all of the hydrogen atom of described any monovalent organic radical group can be replaced by the halogen atom beyond the fluorine atom; S and t represent 0～4 integer respectively independently; B is singly-bound or is selected from the divalent group in the following formula (ii-1)～(ii-8).)
Figure S2006800409604D00102
(in the formula (ii-1), a plurality of R 7Represent independently that respectively halogen atom beyond the hydrogen atom, fluorine atom or carbonatoms are 1～6 alkyl);
Figure S2006800409604D00103
(formula (ii-2) and (ii-3) in, a plurality of R 8And R 9Represent independently that respectively halogen atom beyond the hydrogen atom, fluorine atom or carbonatoms are 1～4 alkyl, u is 4～6 integer);
In the structural unit of (ii) representing with following formula, when B was singly-bound, preferred s and t were 0 or 1 simultaneously.
In the structural unit of (ii) representing with following formula, when B is the divalent group of usefulness following formula (ii-1) expression, preferred R 7It for hydrogen atom, carbonatoms 1～6 alkyl or phenyl.As described carbonatoms is 1～6 alkyl, for example, can enumerate methyl, ethyl, n-propyl, n-hexyl etc.When B for the divalent group of following formula (ii-1) expression the time, preferred s and t are 0 simultaneously, perhaps at least one among s and the t is not 0 and R 6Be the alkyl of carbonatoms 1～10, the cycloalkyl of carbonatoms 6～20, the aryl of carbonatoms 6～20 or the halogen atom beyond the fluorine atom.Among s and the t at least one is not 0 o'clock, as R 6Be preferably methyl, sec.-propyl, the tertiary butyl, cyclohexyl, phenyl, chlorine atom or bromine atoms.As the particularly preferred structural unit of B for the time, can enumerate s and t and represent 0 or 1 and R respectively independently with the divalent group of following formula (ii-1) expression 6And R 7Structural unit for methyl.
In the structural unit of (ii) representing with following formula, when B is the divalent group of usefulness following formula (ii-2) expression, preferred R 8Be the alkyl of carbonatoms 1～4, be preferably methyl especially.When B for the divalent group of following formula (ii-2) expression the time, preferred s and t are 0 simultaneously, perhaps at least one among s and the t is not 0 and R 6Alkyl for carbonatoms 1～10.As above-mentioned R 6The alkyl of carbonatoms 1～10, be preferably methyl especially.As the particularly preferred structural unit of B for the time, can enumerate s and t and represent 0 or 1 and R respectively independently with the divalent group of following formula (ii-2) expression 6And R 8Structural unit for methyl.
In the structural unit of (ii) representing with following formula, when B is the divalent group of usefulness following formula (ii-3) expression, preferred R 9For hydrogen atom or carbonatoms are 1～4 alkyl, be preferably hydrogen atom, methyl or sec.-propyl especially; Preferred u is 4 or 5.When B for the divalent group of following formula (ii-3) expression the time, preferred s and t are 0 simultaneously, perhaps at least one among s and the t is not 0 and R 6Be cyclohexyl.As the particularly preferred structural unit of B for the time, can enumerate s and t and represent 0 or 1 and R respectively independently with the divalent group of following formula (ii-3) expression 6Be cyclohexyl, R 9Be methyl, u is 5 structural unit.
In the structural unit of (ii) representing with following formula, as B during for the divalent group of any one expression in following formula (ii-4)～(ii-8), preferred s and t are 0 simultaneously, and perhaps at least one among s and the t is not 0 and R 6Be the alkyl of carbonatoms 1～10 or the aryl of carbonatoms 6～10.As among s and the t at least one is not 0 o'clock R 6, preferable methyl or phenyl.
As the halogen atom beyond the fluorine atom in the structural unit of (ii) representing with following formula, can enumerate chlorine atom, bromine atoms and iodine atom.
Have with the structural unit of following formula (i) expression and (ii) or the polymkeric substance of the structural unit of (iii) representing with following formula, can by will with the dihydroxy compound of following formula (i ') expression with corresponding to desirable structural unit (ii) or dihydroxy compound (iii), promptly reacted and obtained with compound of representing with following formula (ii ') or (iii ') and polycarbonate precursor:
Figure S2006800409604D00121
(formula (ii ') in, R 6, s, t and B definition and following formula identical in (ii));
Figure S2006800409604D00131
Below, according to the object lesson of the dihydroxy compound of this structural unit of deriving (ii '), the object lesson of the structural unit of (ii) representing with following formula is described.When specific dihydroxy compound (ii ') is reacted with dihydroxy compound (i ') and polycarbonate precursor, obtain having structural unit (i) and corresponding to the structural unit polymkeric substance (ii) of the structure of this dihydroxy compound (ii '), this point, those skilled in the art should be readily appreciated that.
Compound as when the B of following formula in (ii) is singly-bound for example, is preferably 4,4 '-bis-phenol.
Preferred compound when B is formula (ii-1), for example, can enumerate 1, two (4-hydroxy phenyl) methane of 1-, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (those skilled in the art are called " dihydroxyphenyl propane ") of 2-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 2, two (the 4-hydroxy-3-methyl phenyl) propane (those skilled in the art are called " bisphenol-c ") of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-hydroxy phenyl) pentanes of 2-, 2, two (4-hydroxyl-3-phenyl) propane of 2-, 2, two (3-sec.-propyl-4-hydroxy phenyl) propane of 2-, 2, two (3-tert-butyl-hydroxy phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 4, two (4-hydroxy phenyl) heptane of 4-, 2, two (4-hydroxy phenyl) octanes of 2-, 2, two (the 3-bromo-4-hydroxy phenyl) propane of 2-, two (4-hydroxy phenyl) ditan, 2, two (3, the 5-two bromo-4-hydroxy phenyls) propane of 2-, 2,2-two (3,5-two chloro-4-hydroxy phenyls) propane, 2, two (3, the 5-dimethyl-4-hydroxy phenyl) propane of 2-, 2, two (3-hexanaphthene-4-hydroxy phenyl) propane of 2-etc.
Preferred compound when B is formula (ii-2), for example, can enumerate α, α '-two (4-hydroxy phenyl)-adjacent diisopropyl benzene, α, α '-two (4-hydroxy-3-methyl phenyl)-adjacent diisopropyl benzene, α, α '-two (3,5-dimethyl-4-hydroxy phenyl)-adjacent diisopropyl benzene, α, α '-two (4-hydroxy phenyl)-diisopropyl benzene (those skilled in the art are called " bis-phenol M "), α, α '-two (4-hydroxy-3-methyl phenyl)-diisopropyl benzene, α, α '-two (3,5-dimethyl-4-hydroxy phenyl)-diisopropyl benzene, α, α '-two (4-hydroxy phenyl)-to diisopropyl benzene, α, α '-two (4-hydroxy-3-methyl phenyl)-to diisopropyl benzene, α, α '-two (3,5-dimethyl-4-hydroxy phenyl)-to diisopropyl benzene.
Preferred compound when B is formula (ii-3), for example can enumerate 1,1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (4-the hydroxy phenyl)-4-isopropyl methyl hexanaphthenes, 1 of 1-, two (3-cyclohexyl-4-hydroxy phenyl) hexanaphthenes and 1 of 1-, two (4-hydroxy phenyl) pentamethylene of 1-.
When the preferred compound of B when being in the formula (ii-4)～(ii-8) any one, for example, can enumerate two (4-hydroxy phenyl) ethers, two (4-hydroxy-3-methyl phenyl) ether, two (4-hydroxyl-3-phenyl) ether, 4,4 '-dihydroxy benaophenonel, two (4-hydroxy phenyl) sulfide, two (4-hydroxy-3-methyl phenyl) sulfide, two (4-hydroxyl-3-phenyl) sulfide, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy-3-methyl phenyl) sulfoxide, two (4-hydroxyl-3-phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy-3-methyl phenyl) sulfones and two (4-hydroxyl-3-phenyl) sulfone.
Wherein, more preferably B is formula (ii-1), (ii-2), (ii-3) and (ii-6) compound of expression, as particularly preferred compound, in the compound in the time of can enumerating B and be formula (ii-1) 2, two (4-hydroxy phenyl) propane (" dihydroxyphenyl propane "), 2 of 2-, two (the 4-hydroxy-3-methyl phenyl) propane (" bisphenol-c ") and 1 of 2-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-; α in compound when B is formula (ii-2), α '-two (4-hydroxy phenyl)-diisopropyl benzene and α, α '-two (4-hydroxy-3-methyl phenyl)-diisopropyl benzene; In compound when B is formula (ii-3) 1,1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane; And, two (the 4-hydroxy-3-methyl phenyl) sulfide in the compound when B is formula (ii-6).
As the polymkeric substance that uses among the present invention, preferably in following formula (i), p and q are 0, and A is the divalent group with following formula (i-1) expression, R 2Be trifluoromethyl; Preferably following formula (ii) in, B is for following formula (ii-1), (ii-2) or (ii-3) divalent group of expression, when B for the divalent group of following formula (ii-1) expression the time, preferred s and t are 0 or 1 simultaneously, R 6And R 7Be methyl; When B for following formula (ii-2) or (ii-3) during the divalent group of expression, preferred s and t are 0 simultaneously, R 8Be methyl, R 9For hydrogen atom, u are 5.
As object lesson of polymkeric substance so, for example can enumerate the bisphenol AF homopolymer, bisphenol AF/1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane multipolymers of 1-, bisphenol AF/2, two (4-hydroxy phenyl) the propane multipolymers of 2-, bisphenol AF/1,1-bis(4-hydroxyphenyl) cyclohexane multipolymer, bisphenol AF/1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-3-methyl cyclohexanol alkyl copolymer, bisphenol AF/9, two (the 4-hydroxy-3-methyl phenyl) fluorene copolymers of 9-, bisphenol AF/α, α '-two (4-hydroxy phenyl)-diisopropyl benzene multipolymer, bisphenol AF/2, two (4-hydroxy-3-methyl phenyl) propane multipolymers of 2-etc.
The fluorine content weight ratio F of the polymkeric substance that the present invention uses p(the fluorine atom weight that contains in the polymkeric substance is divided by the numerical value of polymer weight) is preferably 0.15～0.60, and more preferably 0.16～0.55, more preferably 0.17～0.50.Therefore, when dihydroxy compound and carbonic ether presoma are reacted, preferably the usage ratio of dihydroxy compound (i ') and dihydroxy compound (ii ') or (iii ') is adjusted, so that the fluorine content weight ratio F in the polymkeric substance of manufacturing pIn above-mentioned scope.Better is, usage ratio to dihydroxy compound (i ') and dihydroxy compound (ii ') or (iii ') is adjusted, so that the structural unit in the polymkeric substance (i) exist ratio with respect to structural unit (i) and structural unit (ii) or summation amount (iii) be preferably 50 moles more than the %, more preferably 75 moles more than the %, more preferably 75～99 moles of % are preferably 75～90 moles of % especially.
Preferably with the reaction of carbonic ether presoma in the purity height of the dihydroxy compound that uses, during with black unit representation once, be preferably below 50, more preferably below 30.The black Ceng Danwei colourity of dihydroxy compound can be measured by the following method, that is, with concentration be the dihydroxy compound solution of 20 weight % as raw material, according to JIS K0071-1, measure by the colorimetry under 25 ℃ temperature.
As mentioned above, when adopting interfacial polymerization or solution polymerization process or melt phase polycondensation that dihydroxy compound and carbonic ether presoma are reacted, thereby the carbonic ether presoma that can use when obtaining having the polymkeric substance with the structural unit of following formula (i) expression for example can be enumerated carboxylic acid halides (Carbonyl halide), carbonic ether (カ one ボ ネ one ト エ ス テ Le) etc.
Described interfacial polymerization can be with dihydroxy compound and carboxylic acid halides, preferably with the dihydroxy compound photoreactive gas at acid binding agent and preferably in the presence of catalyzer, in organic solvent, reacted and carried out.As described acid binding agent, for example, preferably can use the alkali metal hydroxide of sodium hydroxide, potassium hydroxide etc.As organic solvent, for example, preferably can use the halon of methylene dichloride, chlorobenzene etc.As arbitrarily used catalyzer, can enumerate tertiary amine, quaternary ammonium salt, quaternary alkylphosphonium salt etc., as its object lesson, for example, can enumerate triethylamine, four positive fourth ammonium bromides, Si Zheng Ding Ji Phosphonium bromide etc.Preferable reaction temperature is 0～40 ℃, and the reaction times is that the pH in the reaction remains on more than 9 about several minutes～5 hour.
Solution polymerization process can preferably be carried out with the dihydroxy compound photoreactive gas dihydroxy compound and carboxylic acid halides reacting in organic solvent.As acid binding agent as used herein, be preferably aromatic nitrile base, as its object lesson, can enumerate pyridine, quinoline, isoquinoline 99.9, xylidine etc.Wherein, especially preferably use pyridine.As organic solvent, the hydrocarbon of preferred benzene,toluene,xylene etc.; The halon of methylene dichloride, chloroform, ethylene dichloride, chlorobenzene, dichlorobenzene etc. etc., preferred especially methylene dichloride.With respect to carboxylic acid halides 1 equivalent, the usage quantity of preferred acid wedding agent is 2～100 equivalents, more preferably 2～50 equivalents.Preferable reaction temperature is 0～40 ℃, and the reaction times is several minutes～several days, more preferably 10 minutes～5 hours.
Above-mentioned melt phase polycondensation is generally the transesterification reaction of dihydroxy compound and carbonic ether, preferably adopts in the presence of rare gas element, dihydroxy compound and carbonic ether limit heating edge is mixed, and steam the alcohol that generated or the method for phenol.Temperature of reaction is different and different according to the boiling point of alcohol that is generated or phenol, but preferably 120～350 ℃ scope.The preferred reaction time is about 1～10 hour.In the reaction later stage, preferably reaction system is decompressed to about 10～1300Pa, so that carry out steaming of alcohol or phenol easily.As the carbonic ether that can in melt phase polycondensation, preferably use, can enumerate the ester of the aryl of carbonic ether and carbonatoms 6～12, the aralkyl of carbonatoms 7～12, the alkyl of carbonatoms 1～4 etc.Part or all of the hydrogen atom that these aryl, aralkyl, alkyl have can be by replacements such as hydroxyl, halogen atoms.As object lesson of carbonic ether so, for example can enumerate diphenyl carbonate, two (chlorophenyl) carbonic ether, meta-cresol carbonic ether, carbonic acid dinaphthyl ester, two (phenylbenzene) carbonic ether, methylcarbonate, diethyl carbonate, dibutyl carbonate etc., wherein, preferred diphenyl carbonate.
In melt phase polycondensation,, can use polymerizing catalyst in order to accelerate polymerization velocity.As this polymerizing catalyst, can be fit to adopt the catalyzer that in common esterification, transesterification reaction, uses, as its concrete example, for example can enumerate the alkali metal compound of the sodium salt of sodium hydroxide, potassium hydroxide, dihydric phenol, the sylvite of dihydric phenol etc.; The alkali earth metallic compound of calcium hydroxide, hydrated barta, magnesium hydroxide etc.; The nitrogenous basic cpd of Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, Trimethylamine, triethylamine etc.; The alkoxide of basic metal or alkaline-earth metal; The organic acid salt of basic metal or alkaline-earth metal; In addition, can also enumerate zn cpds, boron compound, aluminum compound, silicon compound, germanium compound, organo-tin compound, lead compound, osmium compound, antimony compounds, manganic compound, titanium compound, zirconium compounds etc.These catalyzer both can use separately, also can be used in combination.With respect to the raw material dihydroxy compound, the usage quantity of these polymerizing catalysts is preferably 1 * 10 -9～1 * 10 -2Equivalent is more preferably 1 * 10 -8～5 * 10 -3Normal scope.
In melt phase polycondensation, when using polymerizing catalyst, also can add the catalysis deactivator in the reaction later stage.As this catalysis deactivator, can adopt known catalysis deactivator, but preferably select the catalysis deactivator according to employed catalyzer.For example, when adopting as polymerizing catalyst when being selected from alkali metal compound or the alkali earth metallic compound more than one, the catalysis deactivator for example preferably adopts the ammonium salt or the phosphonium salt of sulfonic acid, more preferably the tosilate of the dodecylbenzene sulfonate of Witco 1298 Soft Acid tetrabutyl phosphonium salt etc. or p-methyl benzenesulfonic acid 4-butyl ammonium etc.In addition, ester as sulfonic acid, can preferably use methyl benzenesulfonate, ethyl benzenesulfonat, Phenylsulfonic acid butyl ester, Phenylsulfonic acid monooctyl ester, Phenylsulfonic acid phenyl ester, p-methyl benzenesulfonic acid methyl esters, p-methyl benzenesulfonic acid ethyl ester, p-methyl benzenesulfonic acid butyl ester, p-methyl benzenesulfonic acid monooctyl ester, p-methyl benzenesulfonic acid phenyl ester etc., wherein, most preferably use Witco 1298 Soft Acid tetrabutyl phosphonium salt.With respect to polymerizing catalyst 1 molar equivalent that is selected from alkali metal hydroxide and alkaline-earth metal oxyhydroxide, the usage quantity of preferred these catalysis deactivators is 0.5～50 mole a ratio, more preferably 0.5～10 mole ratio, more preferably 0.8～5 mole ratio.When carrying out melt polymerization, as required, can also add molecular weight regulator, antioxidant etc.
When above-mentioned dihydroxy compound and carbonic ether presoma react, can use end-capping reagent.As this end-capping reagent, can enumerate the monofunctional phenol that in the polyreaction of polycarbonate, is suitable as end-capping reagent and uses, chloride of acid etc.As described monofunctional phenol, for example, can enumerate phenol, p-tert-butylphenol, to cumenyl phenol, 3,5-two (trifluoromethyl) phenol, Pentafluorophenol, 4-trifluoromethyl-2,3,5,6-polytetrafluoroethylene phenol, fluorophenol, difluorophenol, trifluoromethyl phenol, polytetrafluoroethylene phenol, trifluoromethyl fluorophenol, isooctyl phenol, have the phenol of chain alkyl, have the phenol of aliphatic poly ester group etc. as substituting group as substituting group.As chloride of acid, for example, can enumerate M-nitro benzoic acid muriate, the muriatic derivative of M-nitro benzoic acid, chain alkyl carboxylic acid chloride.These end-capping reagents both can use separately, also can be used in combination.Particularly, when using carboxylic acid halides as the carbonic ether presoma, preferably use under the situation of phosgene, the polymkeric substance that uses these end-capping reagents to obtain, because its end group is by the group end capping from end-capping reagent, therefore, its excellent heat stability.
When the manufacture method of polymkeric substance is interfacial polymerization or solution polymerization process, preferably under the solution state after the polymerization, carries out filtration treatment, thereby remove impurity or foreign matter.When even the manufacture method of polymkeric substance adopts melt phase polycondensation, also can be in appropriate solvent with resulting polymer dissolution, and after carrying out filtration treatment, carry out the separation of polymkeric substance again, be supplied to then in the manufacturing of optical element.
The polymkeric substance that so obtains with structural unit of representing with following formula (i), it is in methylene dichloride, under 20 ℃, the specific viscosity of measuring under the concentration of 0.7g/100mL is preferably 0.1～2.0 scope, more preferably 0.1～0.5 scope, more preferably 0.15～0.3 scope.
The refractive index n of above-mentioned polymkeric substance DWith Abbe number ν DRelation satisfy following formula (I):
n D+0.0076×ν D≤1.78 (I)
Above-mentioned polymkeric substance can be suitable for the optical element raw material of using as achromatic by having the characteristic that satisfies following formula (I).Satisfying following formula (I) means, than the specific refractory power of general plastic material shown in Figure 1 and the universal relation of Abbe number, have a mind to reduce specific refractory power, and mean demonstrate with in the past optics with in the research of plastic material as the opposite characteristic of the high material of the specific refractory power of target.In addition, in the past and do not know that above-mentioned polymkeric substance has this optical characteristics, therefore, those skilled in the art connect do not think aforesaid polymkeric substance suitable as being used for the optical element that achromatic uses.More preferably refractive index n DWith Abbe number ν DRelation satisfy following formula (I '), especially preferably satisfy following formula (I "):
1.65≤n D+0.0076×ν D (I’)
1.73≤n D+0.0076×ν D≤1.78 (I”)。
Described refractive index n DSpecific refractory power under the D line (wavelength 587.56nm) is preferably 1.48～1.58, and more preferably 1.50～1.57, more preferably 1.50～1.54.
Described Abbe number ν DWith following formula (II) expression, be preferably 22～35, more preferably 24～34, more preferably 27～33, be preferably 32～33 especially:
ν D＝(n D-1)/(n F-n C) (II)
(in the formula (II), n DBe the specific refractory power under the D line (wavelength 587.56nm), n FBe the specific refractory power under the F line (wavelength 486.13nm), n cBe the specific refractory power under the C line (wavelength 656.27nm).)
Optical element of the present invention is made of aforesaid polymkeric substance, but as required, can at random contain additive.
As this additive arbitrarily, can enumerate thermo-stabilizer, releasing agent, antioxidant, UV light absorber, bluing agent (bluing), fluorescent coloring, other pigment and antistatic agent etc.
Though the excellent heat stability of above-mentioned polymkeric substance, but have trickleer concave-convex surface shape and have the more optical element of excellent optical in order stably to produce, preferably further improve its thermostability,, can add described thermo-stabilizer for this purpose.As thermo-stabilizer, consider from the viewpoint of the reduction that can suppress the polymericular weight the optical element manufacturing process effectively and foxy, preferably use Phosphorus thermo-stabilizer.
As this Phosphorus thermo-stabilizer, can enumerate bi-ester of phosphite, phosphate compound, phosphinate compound, phosphonate compound and their ester and tertiary phosphine.
As concrete bi-ester of phosphite, for example, can enumerate the triphenyl phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three decyl phosphorous acid esters, the trioctylphosphine phosphorous acid ester, three (octadecyl) phosphorous acid ester, didecyl list phenyl phosphites, dioctyl list phenyl phosphites, di-isopropyl list phenyl phosphites, monobutyl phenylbenzene phosphorous acid ester, single decyl phenylbenzene phosphorous acid ester, single octyl group phenylbenzene phosphorous acid ester, three (diethyl phenyl) phosphorous acid ester, three (diisopropyl phenyl) phosphorous acid ester, three (di-n-butyl phenyl) phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 6-di-tert-butyl-phenyl) phosphorous acid ester, the distearyl pentaerythritol diphosphites, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, two [2, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-] pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, dicyclohexyl pentaerythritol diphosphites etc., in addition, can also enumerate the bi-ester of phosphite that reacts and have ring texture with dihydric phenol.As with dihydric phenol reaction and bi-ester of phosphite with ring texture, for example can enumerate 2 easily, 2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2-di-t-butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester etc.
As phosphate compound, for example can enumerate Tributyl phosphate ester, trimethyl phosphate, three cresyl phosphoric acid ester, triphenyl, trichlorophenyl phosphoric acid ester, triethyl phosphate, diphenylmethyl phenolic group phosphoric acid ester, the adjacent xenyl phosphoric acid ester of phenylbenzene list, three butoxyethyl group phosphoric acid ester, dibutylphosphoric acid ester, dioctyl phosphoric acid ester, di-isopropyl phosphoric acid ester etc., preferred triphenyl or trimethyl phosphate.
As phosphinate compound, for example can enumerate four (2, the 4-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester etc., wherein, preferred four (two-tert-butyl-phenyl)-diphenylenes, two phosphinates or two (two-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2, the 4-di-tert-butyl-phenyl)-diphenylene two phosphinates or two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite ester.This phosphinate compound can have the bi-ester of phosphite and the usefulness of two above substituted aryls with alkyl in the above-mentioned bi-ester of phosphite, and preferably adopts this mode.
As phosphonate compound, for example can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.
As tertiary phosphine, for example, can enumerate triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutyl Phenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three p-methylphenyl phosphines, three naphthyl phosphines, phenylbenzene benzyl phosphine etc.Particularly preferred tertiary phosphine is a triphenylphosphine.
Described thermo-stabilizer, both can only use a kind of, also can be two or more mixing use.Polymkeric substance with respect to 100 weight parts with structural unit of representing with following formula (i), the usage quantity of this thermo-stabilizer is preferably below 0.15 weight part, 0.001～0.15 weight part more preferably, more preferably 0.003～0.1 weight part is preferably 0.005～0.05 weight part especially.
Usually, in optical element, the distortion when preferably reducing moulding as much as possible.In optical element of the present invention, also requirement must reach the transfer printing accurately of surface shape sometimes, and therefore, the distortion when reducing moulding is of crucial importance.From this viewpoint, preferably in described polymkeric substance, add releasing agent.
As this releasing agent, can use various releasing agents, but be the releasing agent that the higher fatty acid ester cpds below the 1ppm constitutes especially preferably in the present invention by sodium content as the releasing agent widespread use of polycarbonate resin.Even this releasing agent is matched with in the described polymkeric substance and at high temperature in addition under the situation of moulding, also can keep good form and aspect.Thus, can under higher hot conditions, carry out moulding, can be with the trickle concaveconvex shape transfer printing exactly of metal die.Its result, surface shape and form and aspect two aspects are all excellent, can obtain accurately bringing into play the optical element of design function.In addition, described sodium content can be measured by following method, that is, the 5g releasing agent is dissolved in the 50ml methylene dichloride, adds the 80ml pure water and stirs, and is in addition quantitative to the sodium amount that finally is dissolved in this pure water with ion chromatography, measures described sodium content thus.
As the higher fatty acid ester cpds, for example, can be by in the presence of the sodium hydroxide catalysts, pure and mild higher fatty acid is reacted and made, can wash fully resultant of reaction by at least a in water or the alcohol, fully reduced the high-grade aliphatic ester of sodium content.
As the higher fatty acid ester cpds, can enumerate the ester cpds of monobasic or polyvalent alcohol and higher fatty acid, the partial esterification compound or the full-cream compound of the monobasic of preferred carbonatoms 1～20 or the saturated fatty acid of polyvalent alcohol and carbonatoms 10～30.As higher fatty acid ester cpds so; for example; can enumerate glyceryl monostearate, Stearinsaeure sorbitol ester, single Glyceryl Behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, stearyl-stearate, palmitoyl cetylate, butyl stearate, Laurate methyl, Wickenol 111, stearic acid 2-ethylhexyl etc.; wherein, preferred glyceryl monostearate or pentaerythritol tetrastearate.In above-mentioned illustration, though all illustrative single compound, these are normally to be utilized with the form of illustrative compound as the mixture of main component.This is because based on following reason: first, higher fatty acid as the high-grade aliphatic ester raw material is made by the natural oil lipid of animal raw fat (shea butter and pig fat) or vegetative grease (plam oil) etc. usually, therefore, it is the mixture that contains other different lipid acid of carbonatoms; The second, there are a lot of free higher fatty acid in institute's synthetic high-grade aliphatic ester; The 3rd, in institute's synthetic high-grade aliphatic ester, there are a lot of unreacted alcohol hydroxyl groups etc.
The acid number of preferred higher fatty acid ester cpds be (can get 0 in fact) below 20, iodine number is (can get 0 in fact) below 10.These characteristics can be obtained according to the method for stipulating among the JIS K0070.
Described releasing agent both can use separately, also can two or more mixing use.
With respect to the polymkeric substance with structural unit of representing with following formula (i) of 100 weight parts, the usage quantity of releasing agent is preferably below 0.5 weight part, more preferably 0.001～0.5 weight part, more preferably 0.005～0.1 weight part.When usage quantity during in this scope, its release property is good, and can not bring the detrimentally affects such as deterioration of the form and aspect of the pollution of the metal die that causes because of releasing agent or moulding product.
In order to prevent the oxidation of optical element of the present invention, can add described antioxidant.As antioxidant, for example can enumerate hindered phenol anti-oxidants, lactone stablizer etc.
As described hindered phenol anti-oxidants, for example, can enumerate triethylene glycol-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic esters], 1, [3-(3 for 6-hexylene glycol-two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], [3-(3 for tetramethylolmethane-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, N, N-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl hydrogenation cinnamic ester), 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 3,9-pair 1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] and ethyl }-2,4,8,10-four oxaspiros (5,5) undecane etc.With respect to the polymkeric substance with structural unit of representing with following formula (i) of 100 weight parts, the usage quantity of these hindered phenol anti-oxidants is preferably below 0.3 weight part, more preferably 0.0001～0.3 weight part, more preferably 0.001～0.1 weight part.
As lipid stablizer in described, for example, can enumerate 3-hydroxyl-5, the resultant of reaction of 7-di-t-butyl-furans-2-ketone and o-Xylol etc.The details of lipid stablizer is open in the flat 7-233160 communique of TOHKEMY in being somebody's turn to do.With respect to the polymkeric substance with structural unit of representing with following formula (i) of 100 weight parts, usage quantity of lipid stablizers is preferably below 0.05 weight part in these, more preferably 0.0005～0.05 weight part, more preferably 0.001～0.03 weight part.
In addition, in addition the blended stablizer is existing sells with interior lipid stablizer and various phosphinate compound and hindered phenol compound, as its preferred example, for example can enumerate the Irganox HP-2921 that CIBASPECIALTY CHEMICALS society makes.
For the weathering resistance that improves optical element of the present invention, cut off deleterious ultraviolet ray, can add described UV light absorber.
As this UV light absorber, can enumerate with 2,2 '-dihydroxyl-4-methoxy benzophenone is the benzophenone UV light absorber of representative; So that 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyloxy phenol is the triazines UV light absorber of representative; With 2-(2H-benzotriazole-2-yl)-4-methylphenol, 2-(2H-benzotriazole-2-yl)-4-tert-octyl phenol, 2-(2H-benzotriazole-2-yl)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-, 2-(2H-benzotriazole-2-yl)-4, the 6-di-tert-pentyl phenol, 2-(5-chloro-2H-benzotriazole-2-yl)-4-methyl-6-tert butyl phenol, 2-(5-chloro-2H-benzotriazole-2-yl)-2, the 4-tert.-butyl phenol, 2,2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethyl butyl) phenol] etc. be the benzotriazole category UV light absorber of representative; With 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone) is the cyclic imino ester class UV light absorber of representative; With 1, two [(2-cyano group-3, the 3-phenylbenzene propylene acyl) oxygen]-2 of 3-, two { [(2-cyano group-3, the 3-phenylbenzene propylene acyl) oxygen] methyl } propane of 2-are the cyanoacrylate UV light absorber of representative etc., further, can also be with two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate etc. uses as UV light absorber for the hindered amine light stabilizer of representative.These UV light absorber or photostabilizer both may be used alone, used in two or more.
With respect to the polymkeric substance with structural unit of representing with following formula (i) of 100 weight parts, the use level of described UV light absorber or photostabilizer is preferably below 5 weight parts, more preferably 0.01～5 weight part, more preferably 0.05～1 weight part.By in above-mentioned scope, using UV light absorber or photostabilizer, can realize requiring the good form and aspect of optical element indispensability and good ultraviolet radiation absorption and shielding properties.
For eliminate optical element owing to polymkeric substance or the additive component yellow that causes of UV light absorber particularly, can add described bluing agent.As bluing agent, just can use so long as be applied to the bluing agent of polycarbonate resin usually.Usually, anthraquinone dyes obtains easily, and is therefore preferred.Its content with respect to polymkeric substance and all the additive total amount be preferably below the 3ppm, 0.1～3ppm more preferably, more preferably 0.3～1.5ppm is preferably 0.3～1.2ppm especially.
For with the light of the wavelength beyond the visible light as visible light use, control achromatic element of the present invention see through light, add described fluorescent coloring.As this fluorescent coloring, for example, can enumerate stilbene compounds, benzimidazole compound, naphthalene imidazolium compounds, rhodamine compound, coumarin kind compound, oxazine compound etc.
For painted, the control of optical element of the present invention sees through light, can add described other pigment.
Optical element of the present invention as required, also contains aforesaid additive arbitrarily by the polymkeric substance formation that has with the structural unit of following formula (i) expression.Optical element of the present invention can be by the polymkeric substance with structural unit of representing with following formula (i) or the mixture of this polymkeric substance and additive, preferably by the melt molding manufactured.
When adopting the melt molding method, the polymkeric substance that preferably will be added with thermo-stabilizer and releasing agent is supplied with the melting mixing machine and is carried out melting mixing, and resulting monofilament is in addition carried out melt molding after the granulating again.That coating of particles can adopt is cylindrical, the suitable shape of elliptical cylinder-shape, corner post shape, sphere etc., but pref. cylindrical or elliptical cylinder-shape.The diameter of cylinder or cylindroid major diameter are preferably 1～5mm, more preferably 1.4～4mm, more preferably 2～3.3mm.When particle is elliptical cylinder-shape, be preferably more than 60% with respect to the ratio of the minor axis of major diameter, more preferably more than 65%.Cylinder or cylindroid length are preferably 1～30mm, more preferably 2～5mm, more preferably 2.5～3.5mm.The ratio of the preferred wherein chip of cutting of particle is few.The ratio of the chip of this cutting is preferably below the 200ppm, more preferably below the 100ppm, more preferably below the 80ppm by the aperture to be the content of chip of cutting of the standard sieve (16 mesh) of 1mm when representing.
Add equably in whole particles that additive can use in the manufacturing of optical element, perhaps, after also can preparing high density ground earlier and containing the master batch of all or part of additive, when making optical element, mixed and used with the particle of the polymkeric substance that does not contain additive.Additive both can be before granulating in advance and polymkeric substance carry out pre-mixing, also polymkeric substance and additive can be added to the melting mixing machine respectively.When with polymeric additive in addition during pre-mixing; can use V-Mixer, Henschel mixer, chemomotive force device, extrude mixing machine etc., premixture also can undertaken re-using after the granulation by extruding granulator or briquetting machine (briquetting machine).If polymkeric substance and additive are added into the melting mixing machine respectively, when additive is liquid additive, can adopts priming device or add liquid device, these additives are supplied with to melt extruding machine.
As the melting mixing machine, preferably adopt forcing machine.As forcing machine, the preferred forcing machine that adopts with the exhaust portion that can outgas to the volatile component of moisture from raw material or the generation of melting mixing resin, and preferably be provided with vacuum pump in exhaust portion, this vacuum pump is used for moisture or volatile component are expelled to the forcing machine outside effectively.In order to promote the discharge of moisture and volatilization composition, can also utilize the water of injection midway at forcing machine, rare gas, nitrogen, carbonic acid gas etc., with the method that outgases after molten resin is mixed.The gas that here is injected into also can be the gas of supercritical state.When carrying out melting mixing, the preferred molten resin is to remove foreign matter by sintered-metal filter etc.It is the following strainers of 10 μ m that strainer preferably uses filtering accuracy.When the second-order transition temperature of employed polymkeric substance as Tg (℃) time, the temperature when preferred molten is mixing is Tg+50 ℃～Tg+250 ℃, the scope of more preferably Tg+80 ℃～Tg+200 ℃.
When resulting monofilament is carried out granulating, can use machines such as tablets press.
For the ratio of the chip of realizing aforesaid preferred cutting, can adopt resulting granules fractionated method in addition, but more preferably use the method for when granulation, the temperature of monofilament being controlled.Promptly; the preferred preparation degree of depth/diameter ratio is about 1.5; volume is the container of the stainless steel more than 1 liter; utilize this container to fill the particle of discharging from tablets press with time of two minutes approximately, the temperature of control monofilament is after using this container to fill particle; the particulate temperature of thermopair being inserted the central part of this container at once and measuring; with with the second-order transition temperature of employed polymkeric substance as Tg (℃) time, reach Tg-30 ℃～Tg-15 ℃, be preferably Tg-27 ℃～Tg-18 ℃.When this temperature surpasses Tg-15 ℃, cause particle stickup each other sometimes, when being lower than Tg-30 ℃, cause the increase of cutting chip ratio sometimes easily.
When to polymkeric substance or when the composition that polymkeric substance adds above-mentioned additive arbitrarily carries out granulating; in order to reduce foreign matter or impurity as far as possible; preferably manufacturing installations such as melting mixing machine or tablets press are arranged in the air ambient of cleaning; the foreign matter amount of the water coolant that preferred minimizing water cooler is used; further, preferably fill raw material supplying hopper, raw material supplying stream, particle hold tank etc. with clean air.For example, the also preferred method of in the flat 11-21357 communique of TOHKEMY, proposing that adopts.In addition,, be fit to adopt rare gas elementes such as nitrogen are flowed in the manufacturing installation, cut off the method for oxygen thus as the method for the form and aspect of improving resulting optical element.
Preferably the particle that will obtain as mentioned above is kept in the encloses container, and supplies with in the melt molding.
Then use the melt molding method, give shape, thereby obtain optical element of the present invention resulting granules.As the melt molding method, for example, can enumerate injection moulding, extrusion moulding etc.
Described injection moulding, it is the notion that comprises the fill method that is referred to as flowing forming (Flow-Moulding), except common forming method, according to purpose can also suitably use compression molding, injection pressure moulding, gas assistant formation, foaming (comprising), insert moulding by injecting the moulding of supercutical fluid, in-mold coating moulding, heat insulating mold moulding, the technology of heating cooling mould molding, dual-color forming, interlayer moulding, ultra-high speed injection molding etc. rapidly.In addition, after can also adopting the thick finished product of manufacturing, form the method for micro concavo-convex or take out the die insert (going into れ) that is used to form moulding rear chamber thereby carry out extrusion forming again, in this die insert (going into れ), carry out anneal, take out the method for moulding product etc. then.Injection molding can be adopted any one in cold runner mode and the hot runner mode.In described injection molding, when will have with the second-order transition temperature of the polymkeric substance of the structural unit of above-mentioned (i) expression as Tg (℃) time, barrel temperature is preferably Tg+80 ℃～Tg+250 ℃, the scope of more preferably Tg+100 ℃～Tg+220 ℃; Die temperature is preferably Tg-100 ℃～Tg-50 ℃, the scope of more preferably Tg-60 ℃～Tg-15 ℃.
As described extrusion moulding, can adopt known method in the past.When concaveconvex shape is given on moulding product surface, the method that can adopt the method for giving, give by cooling roller, method of extrusion forming etc. that resulting extrusion molding article carried out by mold shape.
Optical element of the present invention after the surface treatment of as required, can carry out hard coat to its surface, prevent reflectance coating, antifogging coating etc. is suitable, is applied again.
The optical element of the present invention that so obtains is with respect to its first surface with as the formed body that has very little thickness for the second surface of the reverse side of this first surface and their maximum diameter.As the shape of first surface and second surface, for example can enumerate circle, have the polygon on 3～20 summits etc.The maximum diameter on described surface when surface shape is circle, is meant its diameter, when surface shape is polygon, is meant distance maximum in its diagonal lines.The thickness of optical element of the present invention is preferably 0.001～0.2 with respect to the maximum diameter on surface, and more preferably 0.01～0.1.
The first surface of optical element of the present invention and at least one face in the second surface are on-plane surface, for example, can be the single curved surface (part of sphere) with certain radius-of-curvature or the combination of a plurality of curved surfaces, perhaps, be the face with concavo-convex or stairstepping of rule.
Described maximum diameter can suitably be set according to purposes, for example, can be 0.1～1000mm, more preferably 1～100mm.
Optical element of the present invention can be used in the achromatic of the achromatic lens system that is made of a plurality of optical elements (lens) or achromatic lens.In the optical element of other that use with optical element combination of the present invention at least one, preferred Abbe number ν DBe 50～60, refractive index n DIt is 1.48～1.55 material.As optical element so, can enumerate the optical element that constitutes by at least a material that is selected among the group that glass, thermosetting resin, thermoplastic resin and uv curing resin form.As described thermosetting resin, for example can enumerate epoxy acrylate; As described thermoplastic resin, for example can enumerate polymethylmethacrylate, poly-cyclic olefin etc.As the commercially available product of poly-cyclic olefin, for example, can preferably enumerate ゼ オ ネ Star Network ス (ZEONEX, Japanese ZEON (strain) makes), ア one ト Application (ARTON, JSR (strain) makes), ア ペ Le (APER, Mitsui Chemicals (strain) is made) etc.Wherein, as other the optical element material that uses with optical element combination of the present invention, preferred thermoplastic resin, preferred especially plexiglass.
Achromatic lens system or achromatic lens are made of optical element of the present invention and aforesaid other optical element.As other optical element, for example can enumerate convex lens, Fresnel lens, diffraction grating etc.As convex lens, both can be spherical lens, also can be non-spherical lens, both can be biconvex lens, also can be the single face convex lens.With the optical element of the present invention that aforesaid other optical element combination is used, for example can be concave mirror, Fresnel lens, diffraction grating etc.As concave mirror, both can be spherical lens, also can be non-spherical lens, both can be biconcave lens, also can be the single face concave mirror.
As the achromatic lens system that is used in optical element of the present invention, can enumerate achromatic lens system that constitutes by separated a plurality of optical elements etc., as achromatic lens, then can enumerate cascade type achromatic lens etc.
As the described achromatic lens system that constitutes by separated a plurality of optical elements, for example can enumerate the achromatic lens system that forms by convex lens and concave mirror.So one of achromatic lens system is illustrated among Fig. 2.Achromatic lens system shown in Figure 2 is by constituting as other optical elements 1 of convex lens with as the optical element of the present invention 2 of concave mirror.Being centered close to coaxial and separating suitable distance and be provided with and be used of preferred these two lens.Light is from the incident of convex lens side, and in the further right side imaging of concave mirror.
As described cascade type achromatic lens, can enumerate achromatism revisal lens (AchromaticLens), cascade type diffraction lens etc.
Achromatism revisal lens be be referred to as crown glass the convex lens shape optical element and have with it the achromatic lens that the optical element that is referred to as flint glass of the face that coincide is laminated.The one of preferred of achromatism revisal lens is illustrated among Fig. 3.The achromatism revisal lens of Fig. 3 be as crown glass other optical element 3 and be laminated as the optical element of the present invention 4 of flint glass.At this moment, light is from crown glass 3 side incidents, and in the further right side imaging of flint glass 4.
The cascade type diffraction lens is laminated with optical element of the present invention with by other optical elements that aforesaid material constitutes, and is meant that its interface is formed with the lens of fine three-dimensional shape.As this three-dimensional shape, for example can enumerate stairstepping, Jino shape (kinoform), jagged embossing pattern etc.By the cascade type diffraction lens is made by achromatic lens of the present invention system, can carry out achromatic very effectively, the focal length behind the achromatic extremely shortens than known achromatic lens system in the past.As the stacked diffraction lens that can be suitable for optical element of the present invention, for example, can enumerate the stacked diffraction lens of record in TOHKEMY 2003-315524 number, TOHKEMY 2004-212495 number etc.
One of preferred stacked diffraction lens is illustrated among Fig. 4.The stacked diffraction lens of Fig. 4 is that optical element 5 of the present invention and other optical elements 6 are laminated, and its interface forms stepped.The stairstepping at the stacked diffraction lens interface of Fig. 4, has ladder about five sections from the center of lens to periphery, but Fig. 4 is a synoptic diagram, in the stacked diffraction lens of reality, the stagewise cycle is preferably about 1～300 μ m, and the stagewise hop count can be regarded as the hop count of being calculated by the diameter of described cycle and lens.
Be suitable for the aforesaid achromatic lens system or the achromatic lens of optical element of the present invention, it is in light weight, and focal length is shortened, and is particularly suitable for and is combined in the telephoto lens system of the camera of analog or digital or pick up camera etc. or the super telephoto lens system using.
Embodiment
Among below each embodiment and comparative example, the black of using as polymer raw material of dihydroxy compound once was worth, be by with concentration be each dihydroxy compound solution of 20 weight % as sample, according to JIS K0071-1, measure down at 25 ℃ with colorimetry.As the solvent that in the preparation of solution, uses, when dihydroxy compound is 1, during the 1-bis(4-hydroxyphenyl) cyclohexane acetone, the next use methyl alcohol of other situation.
The specific viscosity of synthetic polymkeric substance in each embodiment and the comparative example, then with the dichloromethane solution (concentration is 0.7g/100ml) of polymkeric substance as sample, measure down at 20 ℃.
In addition, in following, " Tg " be employed polymkeric substance second-order transition temperature (℃).
[preparation example of releasing agent]
Preparation example 1
The glycerine and the stearic acid of the reagent superfine that will make with the pure medicine of light (strain) react in the presence of sodium hydroxide catalyst by usual method, obtain glyceryl monostearate.Sodium content at the glyceryl monostearate of this preparation is 9.8ppm.
Preparation example 2
The glyceryl monostearate composition that obtains in the above-mentioned preparation example 1 is fully washed, thereby the preparation sodium content is the glyceryl monostearate of 0.2ppm.
Embodiment 1
[synthesizing of polymkeric substance]
Thermometer is being installed, in the reactor of stirrer and reflux exchanger, add aqueous sodium hydroxide solution 79.0 weight parts of ion exchanged water 460.1 weight parts and 48 weight %, then add black Ceng Danwei colourity and be 30 2, two (the 4-hydroxy phenyls)-1 of 2-, 1,1,3,3,3-HFC-236fa 82.1 weight parts (76.5 moles of % of dihydroxy compound total amount), black Ceng Danwei colourity be 20 2, two (4-hydroxy-3-methyl phenyl) propane 19.2 weight parts (23.5 moles of % of dihydroxy compound total amount) of 2-and hydrosulphite (hydrosulphite) 0.20 weight part and dissolved, after adding methylene dichloride 271.3 weight parts again, stir and 15～20 ℃ temperature under with being blown into phosgene 41.1 weight parts in 60 minutes.Phosgene be blown into end after, add aqueous sodium hydroxide solution 18.4 weight parts of p-tert-butylphenol 2.9 weight parts and 48 weight % and carry out emulsification, then, add triethylamine 0.1 weight part, and stirred one hour down and finish reaction at 28～33 ℃.Reaction is diluted resultant after finishing with methylene dichloride, with ion-exchange water washing dichloromethane layer, become neutrality until washings, wash with dilute hydrochloric acid then, further wash repeatedly, much at one until the electric conductivity of the electric conductivity of water layer and ion exchanged water with ion exchanged water.Removing solvent from dichloromethane layer, is 0.19 polymkeric substance 1 (polycarbonate) (yield is 95%) thereby obtain specific viscosity.
[making of polymer beads]
The polymkeric substance 1 that obtains in above-mentioned [polymkeric substance synthetic] carried out 5 hours warm air drying under 120 ℃.In 100 parts by weight polymer 1 after warm air drying, driedly mix up for three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.01 weight parts of stablizer and be glyceryl monostearate 0.05 weight part of 0.2ppm as the sodium content by above-mentioned preparation example 2 preparations of releasing agent.
To this mixture, use has the exhaust biaxial extruder (model: TEX30 α-XSST of disc filter, complete meshing type, equidirectional rotation, double thread screw rod, (strain) JSW makes), at extrusion capacity is that 20kg/h, screw rod revolution are that 180rpm, exhaust portion vacuum tightness are that 3kPa, extrusion temperature have under the condition of the interim temperature configuration that rises between the Tg+100 ℃～Tg+120 ℃ extruded monofilament.To the monofilament extruded in addition after the water cooling with the tablets press cutting, producing major diameter is that 3.4mm, minor axis are that 2.3mm and length are the particle of the elliptical cylinder-shape of 2.7mm.At this moment; temperature and dipping time to the water cooler that is used for the water cooling monofilament are regulated; with use the degree of depth/diameter ratio be about 1.5 and volume be that 1 liter stainless steel container made receives the particle of discharging from tablets press; through after about two minutes containers fill, immediately thermopair is inserted these container central authorities and the temperature measured in the scope of Tg-30 ℃～Tg-25 ℃.
Be supplied in the injection molding after 5 hours the drying under 120 ℃ the particle that obtains at this being carried out with the cleaning baking oven.
[evaluation of optical characteristics]
With the above-mentioned pellet supply that obtains is in the injection moulding machine of 147kN to mold clamping pressure, and to set barrel temperature be that Tg+130 ℃, die temperature are Tg-35 ℃, the level and smooth tabular test piece of the long 90mm of moulding, wide 50mm and thick 2mm.
With the colour-difference meter (SE2000) that the electric look of Japan (strain) is made, the form and aspect (b value) of resulting test piece are measured, its result is 1.8.
In addition, the Abb made from (strain) ア タ go, and serve as contact liquid with the bromination naphthalene, at 23 ℃ of Abbe number ν that measure this test piece down DAnd specific refractory power, its result, Abbe number ν DBe 32, refractive index n DBe 1.52.With the left side (X in these numerical evaluation following formulas (I) p=n D+ 0.0076 * ν D) numerical value, its result is 1.76, satisfies following formula (I).
Embodiment 2～25, comparative example 1～3
In [the synthesizing of polymkeric substance] of embodiment 1, except respectively the compound of table 1 record being pressed the described ratio of mixture use of table 1 as dihydroxy compound, carry out 1 identical operations with embodiment, thereby synthetic polymer 2～28, and use institute's synthetic polymkeric substance respectively, operate similarly to Example 1 and make particle, carry out various evaluations.
In addition, in [making of polymer beads] of embodiment 16, use the glyceryl monostearate of the sodium content of preparation in above-mentioned preparation example 1 as 9.8ppm as releasing agent.
Show the result in the table 1.
Comparative example 4
In the reactive tank that is provided with whipping appts, distiller and reliever, drop into black Ceng Danwei colourity and be 20 1,4-cyclohexanedimethanol 43.2 weight parts (50 moles of % of dihydroxy compound total amount), black Ceng Danwei colourity be 10 2, two (4-hydroxy phenyl) propane 68.4 weight parts (50 moles of % of dihydroxy compound total amount) of 2-, diphenyl carbonate 134.96 weight parts, Tetramethylammonium hydroxide 0.18 weight part and sodium hydroxide 8 * 10 -4Weight part ℃ carries out fusion at nitrogen replacement post-heating to 140.Stir after 30 minutes, Yi Bian slowly reduced pressure in interior temperature rise to 180 ℃ one side, under 13.3kPa, carry out 30 minutes reaction, boil off the phenol that is generated.Then, heat up keeping under the situation of this pressure, 190 ℃ following 30 minutes, 200 ℃ following 40 minutes, 220 ℃ following 30 minutes and made it reaction in the distillation phenol in following 30 minutes at 240 ℃.Then, slowly decompression is decompressed to pressure below the 133Pa.Keep this pressure and 240 ℃ of further lasting down stirrings 4 hours, thereby obtaining polymkeric substance 29.
With the above-mentioned polymkeric substance that obtains 29, make particle similarly to Example 1, and carry out various evaluations.Show the result in the table 1.
In the table 1, the symbol of expression dihydroxy compound is represented following implication respectively, and the arithemetic unit on each hurdle of dihydroxy compound is mole %.In addition, "-" expression does not have to use the dihydroxy compound corresponding to this hurdle.
BP-AF-1: black Ceng Danwei colourity be 30 2, two (the 4-hydroxy phenyls)-1,1,1,3,3 of 2-, the 3-HFC-236fa [is equivalent to the fluorine content weight ratio F in the structural unit of general formula (i) W=0.31]
BP-AF-2: black Ceng Danwei colourity be 10 2, two (the 4-hydroxy phenyls)-1,1,1,3,3 of 2-, the 3-HFC-236fa [is equivalent to the fluorine content weight ratio F in the structural unit of general formula (i) W=0.31]
BP-C: black Ceng Danwei colourity be 20 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-
BP-AP: black Ceng Danwei colourity be 20 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-
BP-A: black Ceng Danwei colourity be 10 2, two (4-hydroxy phenyl) propane of 2-
BP-Z: black Ceng Danwei colourity be 10 1, the 1-bis(4-hydroxyphenyl) cyclohexane
BP-TMC: black Ceng Danwei colourity be 10 1, two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane
BC-S: black Ceng Danwei colourity is two (4-hydroxy-3-methyl phenyl) sulfide of 50
BC-F: black Ceng Danwei colourity be 20 9, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-
BP-M: black Ceng Danwei colourity is 10 α, α '-two (4-hydroxy phenyl)-diisopropyl benzene
BC-M: black Ceng Danwei colourity is 50 α, α '-two (4-hydroxy-3-methyl phenyl)-diisopropyl benzene
CHDM: black Ceng Danwei colourity is 20 1,4 cyclohexane dimethanol
Table 1
Figure S2006800409604D00321
Table 1 (continuing)
Figure S2006800409604D00331
Table 1 (continuing)
Figure S2006800409604D00341
Table 1 (continuing)
Figure S2006800409604D00351
As the evaluation of achromatic with optical element
Calculated example 1
In order to verify the effect of optical element of the present invention, under the following conditions, calculate the focal length of F line (wavelength 486.13nm) and C line (wavelength 656.27nm).
Will be by plexiglass (ν D=57, n D=1.491, n F=1.496, n C=1.488) convex lens of Gou Chenging (radius-of-curvature of the curved surface of bore 60mm, light entrance face is+radius-of-curvature of the curved surface of 120mm, light-emitting face is-80mm, the maximum ga(u)ge of lens centre is 20mm) and the concave mirror that constitutes of the polymkeric substance of making by the foregoing description 99 (radius-of-curvature of the curved surface of bore 60mm, light entrance face is-550mm for the radius-of-curvature of the curved surface of-80mm, light-emitting face, the minimum thickness of lens centre is 5mm) connect airtight and fit together as the cascade type lens, the convex lens side is calculated the focal length of F line and C line as light incident side.In the calculating of this focal length, used " lens design, Performance of Optical System assessment process POPS 0.0.7 " (can be from network address URL:http: //www.vector.co.jp/soft/win95/edu/sel136306.html obtains.Retrieval on October 25th, 2006).
Calculation result is shown in Table 2 with the F line of the polymkeric substance that has used concave mirror and the specific refractory power of C line.
Calculated example 2～7, comparison calculated example 1～3
In calculated example 1, replace operate the focal length of calculating F line and C line equally with calculated example 1 the concave mirror that polymkeric substance 9 constitutes except using polymkeric substance by table 2 record respectively.
Calculation result is shown in Table 2 with the F line of the polymkeric substance that is used for concave mirror and the specific refractory power of C line.
Table 2

Claims (11)

1. an achromatic lens is characterized in that, by the structural unit that has with following general formula (i) expression, and refractive index n DWith Abbe number ν DRelation satisfy the optical element that the polymkeric substance of following formula (I) constitutes, and use Abbe number ν DBe 50～60, refractive index n DBe that other the optical element that 1.48～1.55 material constitutes constitutes:
n D+0.0076×ν D≤1.78 (I)；
Figure FSB00000332008200011
In the formula (i), a plurality of R 1Being independently selected from respectively by carbonatoms is that 1～10 alkyl, carbonatoms are that 1～10 alkoxyl group, carbonatoms are that 6～20 cycloalkyl, carbonatoms are that 6～20 cycloalkyloxy, carbonatoms are 6～10 aryl, carbonatoms is that 7～20 aralkyl, carbonatoms are that 6～10 aryloxy and carbonatoms are any monovalent organic radical group or the halogen atom among the group that forms of 7～20 aralkoxy, and part or all of the hydrogen atom in the described any monovalent organic radical group replaced or do not replaced by halogen atom by halogen atom; P and q represent 0～4 integer respectively independently; A is singly-bound or is selected from the divalent group in the following formula (i-1)～(i-4) that wherein, when A was the divalent group of singly-bound or non-contain fluorine atoms, p and q were not 0 simultaneously, the R that exists in the formula (i) 1At least one be any monovalent organic radical group or fluorine atom, part or all of the hydrogen atom of described any monovalent organic radical group replaced by fluorine atom;
Figure FSB00000332008200012
In the formula (i-1), a plurality of R 2Part or all carbonatoms that is replaced by halogen atom or do not replaced by halogen atom of representing hydrogen atom, halogen atom or hydrogen atom respectively independently is 1～10 alkyl;
Figure FSB00000332008200021
In the formula (i-2)～(i-4), a plurality of R 3, R 4And R 5Part or all carbonatoms that is replaced by halogen atom or do not replaced by halogen atom of representing hydrogen atom, halogen atom or hydrogen atom respectively independently is 1～4 alkyl, and the r in the formula (i-3) is 4～11 integer.
2. achromatic lens as claimed in claim 1, wherein, the Abbe number ν of above-mentioned polymkeric substance DBe 22～35.
3. achromatic lens as claimed in claim 1, wherein, the refractive index n of above-mentioned polymkeric substance DBe 1.48～1.58.
4. achromatic lens as claimed in claim 1, wherein, above-mentioned with the fluorine content weight ratio F in the structural unit of formula (i) expression MBe 0.22～0.63.
5. achromatic lens as claimed in claim 1, wherein, the fluorine content weight ratio F in the above-mentioned polymkeric substance pBe 0.15～0.60.
6. achromatic lens as claimed in claim 1, wherein, above-mentioned structural unit with formula (i) expression is from 2, two (the 4-hydroxy phenyls)-1,1,1,3,3 of 2-, 3-HFC-236fa deutero-structural unit.
7. achromatic lens as claimed in claim 1, wherein, above-mentioned polymkeric substance is except the structural unit with formula (i) expression, also have other structural units, and, with respect to the summation amount of structural unit and other structural units of formula (i) expression, the content of the structural unit that polymkeric substance contains (i) is 75 moles more than the %.
8. achromatic lens as claimed in claim 1, wherein, above-mentioned polymkeric substance also has with following formula (ii) or the structural unit of (iii) representing:
Figure FSB00000332008200031
Formula (ii) in, a plurality of R 6Being independently selected from respectively by carbonatoms is 1～10 alkyl, carbonatoms is 1～10 alkoxyl group, carbonatoms is 6～20 cycloalkyl, carbonatoms is 6～20 cycloalkyloxy, carbonatoms is 6～10 aryl, carbonatoms is 7～20 aralkyl, carbonatoms is that 6～10 aryloxy and carbonatoms are any monovalent organic radical group among the group that forms of 7～20 aralkoxy or the halogen atom beyond the fluorine atom, and part or all of the hydrogen atom in the described any monovalent organic radical group replaced by the halogen atom beyond the fluorine atom or be not substituted; S and t represent 0～4 integer respectively independently; B is singly-bound or is selected from divalent group in the following formula (ii-1)～(ii-8);
Figure FSB00000332008200032
In the formula (ii-1), a plurality of R 7Represent independently that respectively halogen atom beyond the hydrogen atom, fluorine atom or carbonatoms are 1～6 alkyl;
Figure FSB00000332008200033
Formula (ii-2) and (ii-3) in, a plurality of R 8And R 9Represent independently that respectively halogen atom beyond the hydrogen atom, fluorine atom or carbonatoms are 1～4 alkyl, u is 4～6 integer;
Figure FSB00000332008200041
9. achromatic lens as claimed in claim 8, wherein,
In the described formula (i), p and q are 0, and A is the divalent group with described formula (i-1) expression, R 2Be trifluoromethyl;
Described formula (ii) in, B is for described formula (ii-1), (ii-2) or the divalent group (ii-3) represented;
As B during for the divalent group represented with described formula (ii-1), s and t are 0 or 1 simultaneously, R 6And R 7Be methyl;
When B for described formula (ii-2) or during the divalent group of (ii-3) representing, s and t are 0 simultaneously, R 8Methyl, R 9Be hydrogen atom, u is 5;
With respect to structural unit (i) and structural unit (ii) or structural unit summation amount (iii), it is 75 moles more than the % with the content of the structural unit of described formula (i) expression;
And the Abbe number ν of above-mentioned polymkeric substance DBe 27～33, refractive index n DBe 1.50～1.54.
10. achromatic lens as claimed in claim 9, wherein, above-mentioned polymkeric substance is the bisphenol AF homopolymer, bisphenol AF/1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane multipolymers of 1-, bisphenol AF/2, two (4-hydroxy phenyl) the propane multipolymers of 2-, bisphenol AF/1,1-bis(4-hydroxyphenyl) cyclohexane multipolymer, bisphenol AF/1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-3-methyl cyclohexanol alkyl copolymer, bisphenol AF/9, two (the 4-hydroxy-3-methyl phenyl) fluorene copolymers of 9-, bisphenol AF/α, α '-two (4-hydroxy phenyl)-diisopropyl benzene multipolymer or bisphenol AF/2, two (4-hydroxy-3-methyl phenyl) the propane multipolymers of 2-.
11. achromatic lens as claimed in claim 1, wherein, achromatic lens is the cascade type achromatic lens.
CN2006800409604A 2005-11-10 2006-11-08 Optical device and achromatic lens Active CN101300286B (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2005325997 2005-11-10
JP2005325996 2005-11-10
JP325998/2005 2005-11-10
JP325997/2005 2005-11-10
JP325996/2005 2005-11-10
JP2005325998 2005-11-10
PCT/JP2006/322691 WO2007055390A1 (en) 2005-11-10 2006-11-08 Optical device and achromatic lens

Publications (2)

Publication Number Publication Date
CN101300286A CN101300286A (en) 2008-11-05
CN101300286B true CN101300286B (en) 2011-03-30

Family

ID=38023379

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2006800409604A Active CN101300286B (en) 2005-11-10 2006-11-08 Optical device and achromatic lens

Country Status (7)

Country Link
US (1) US7700714B2 (en)
EP (1) EP1947131A4 (en)
JP (1) JPWO2007055390A1 (en)
KR (1) KR101288726B1 (en)
CN (1) CN101300286B (en)
TW (1) TWI405998B (en)
WO (1) WO2007055390A1 (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101680967B (en) * 2007-08-27 2012-01-25 帝人化成株式会社 Lens and optical unit using the same
JP5714788B2 (en) * 2007-09-10 2015-05-07 帝人株式会社 Plastic lens and manufacturing method thereof
CN102307930B (en) * 2009-03-06 2013-07-24 帝人化成株式会社 Copolycarbonate and optical lens
JP5266599B2 (en) * 2009-04-24 2013-08-21 帝人株式会社 High refractive index polycarbonate copolymer
KR101881616B1 (en) * 2011-01-14 2018-07-24 데이진 가부시키가이샤 Optical lens comprising aromatic-aliphatic polycarbonate resin
JP5962129B2 (en) * 2011-03-31 2016-08-03 三菱化学株式会社 Method for producing polycarbonate resin
KR101297365B1 (en) * 2011-09-16 2013-08-14 롯데케미칼 주식회사 Polycarbonate terpolymer, method for preparing the same and molded article using the same
KR101491781B1 (en) * 2012-06-28 2015-02-24 한양대학교 산학협력단 Polycarbonate terpolymer, and molded article using the same
JP6468748B2 (en) * 2014-07-28 2019-02-13 オリンパス株式会社 Composite optical element manufacturing apparatus and composite optical element manufacturing method
WO2016137445A1 (en) * 2015-02-24 2016-09-01 South Dakota Board Of Regents Polycarbonates having superior dielectric properties suitable for energy dense capacitors
WO2016147847A1 (en) * 2015-03-13 2016-09-22 大阪ガスケミカル株式会社 Resin composition and optical lens
WO2017115649A1 (en) 2015-12-28 2017-07-06 富士フイルム株式会社 Compound, curable composition, cured article, optical member, and lens
JP6712633B2 (en) * 2016-02-23 2020-06-24 富士フイルム株式会社 Polycarbonate resin, molded body, optical member and lens
JP6670923B2 (en) 2016-02-24 2020-03-25 富士フイルム株式会社 Polycarbonate resin, molded body, optical member and lens
JP6851775B2 (en) * 2016-10-31 2021-03-31 キヤノン株式会社 Diffractive optical element and optical system having it, imaging device
US11086062B2 (en) * 2017-03-31 2021-08-10 Fukuvi Chemical Industry Co., Ltd. Circumferentially light-emitting type thermoplastic resin molded body
KR101962034B1 (en) * 2017-10-25 2019-03-25 한국기초과학지원연구원 Broadband objective lens with anti-reflective nanopatterns and a manufacturing method thereof
TWI776002B (en) * 2017-12-28 2022-09-01 日商三菱瓦斯化學股份有限公司 Optical resin material and optical element for chromatic aberration correction
JP2020126162A (en) * 2019-02-05 2020-08-20 三菱ケミカル株式会社 Image display light guide plate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5475786A (en) * 1992-11-02 1995-12-12 The Furukawa Electric Co., Ltd. Aromatic polycarbonate copolymer, a process for producing the same, and a plastic optical waveguide using the same
CN1388905A (en) * 2000-07-11 2003-01-01 帝人化成株式会社 Plastic lens

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6218501A (en) 1985-07-18 1987-01-27 Teijin Chem Ltd Optical formed article
JPS6431825A (en) 1987-07-28 1989-02-02 Mitsubishi Chem Ind Material for optical parts formation
JPH053625Y2 (en) 1987-08-21 1993-01-28
JPH0361911A (en) 1989-07-31 1991-03-18 Furukawa Electric Co Ltd:The Heat resistant plastic optical fiber
JP3183359B2 (en) 1992-04-22 2001-07-09 出光石油化学株式会社 Printing device card holder
JP3150456B2 (en) * 1992-11-02 2001-03-26 帝人化成株式会社 Method for producing aromatic polycarbonate copolymer
JPH06200005A (en) 1992-11-02 1994-07-19 Teijin Chem Ltd Aromatic polycarbonate copolymer
US5409975A (en) * 1992-11-02 1995-04-25 The Furukawa Electric Co., Ltd. Aromatic polycarbonate copolymer, a process for producing the same, and a plastic optical waveguide using the same
JP3155092B2 (en) * 1992-11-02 2001-04-09 帝人化成株式会社 Method for producing aromatic polycarbonate copolymer
JP3133548B2 (en) 1993-03-26 2001-02-13 キヤノン株式会社 Electrophotographic photoreceptor and electrophotographic apparatus provided with the electrophotographic photoreceptor
JPH06347650A (en) 1993-04-12 1994-12-22 Furukawa Electric Co Ltd:The Plastic light transmission body and its production
JP3717555B2 (en) 1994-09-12 2005-11-16 オリンパス株式会社 Diffractive optical element
US5847877A (en) * 1994-09-12 1998-12-08 Olympus Optical Co., Ltd. Diffractive optical element
US6781756B1 (en) * 1995-08-29 2004-08-24 Olympus Corporation Diffractive optical element
JP3618464B2 (en) 1995-08-29 2005-02-09 オリンパス株式会社 Diffractive optical element and optical apparatus using the same
JP2000071266A (en) * 1998-09-02 2000-03-07 Teijin Chem Ltd Production of aromatic polycarbonate resin molding
JP3517625B2 (en) * 1999-07-01 2004-04-12 キヤノン株式会社 Optical material and optical system using the same
JP2003192780A (en) * 2001-12-27 2003-07-09 Mitsui Chemicals Inc Molding material for optical part
KR100894936B1 (en) * 2002-01-23 2009-04-27 이데미쓰 고산 가부시키가이샤 Aromatic polycarbonate resin, process for producing the same, optical-part molding material, and optical part
EP1376161B1 (en) * 2002-06-17 2008-10-15 Canon Kabushiki Kaisha Diffractive optical element and optical system provided with the same
JP4006362B2 (en) 2002-06-17 2007-11-14 キヤノン株式会社 Diffractive optical element and optical system having the same
JP4051549B2 (en) * 2002-08-14 2008-02-27 三菱瓦斯化学株式会社 Polycarbonate resin composition
KR100956048B1 (en) * 2002-11-14 2010-05-06 테이진 카세이 가부시키가이샤 Polycarbonate copolymer, resin composition, and molded article
JP3940086B2 (en) 2003-02-06 2007-07-04 共栄社化学株式会社 Fluorine-substituted alicyclic group-containing (meth) acrylic acid ester and cured product thereof
JP4316959B2 (en) 2003-08-20 2009-08-19 出光興産株式会社 Polycarbonate copolymer, method for producing the same, and optical member
JP2005107298A (en) * 2003-09-30 2005-04-21 Nikon Corp Diffraction optical element and method for manufacturing the same
JP2005292184A (en) * 2004-03-31 2005-10-20 Fuji Photo Film Co Ltd Optical unit
WO2005100443A1 (en) * 2004-04-14 2005-10-27 Idemitsu Kosan Co., Ltd. Sulfur-containing compound, method for producing same, sulfur-containing polymer, and optical material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5475786A (en) * 1992-11-02 1995-12-12 The Furukawa Electric Co., Ltd. Aromatic polycarbonate copolymer, a process for producing the same, and a plastic optical waveguide using the same
CN1388905A (en) * 2000-07-11 2003-01-01 帝人化成株式会社 Plastic lens

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JP昭62-18501A 1987.01.27
JP特开2003-315524A 2003.11.06

Also Published As

Publication number Publication date
JPWO2007055390A1 (en) 2009-04-30
TWI405998B (en) 2013-08-21
WO2007055390A1 (en) 2007-05-18
US7700714B2 (en) 2010-04-20
EP1947131A4 (en) 2010-10-27
CN101300286A (en) 2008-11-05
TW200730864A (en) 2007-08-16
EP1947131A1 (en) 2008-07-23
KR20080066029A (en) 2008-07-15
KR101288726B1 (en) 2013-07-23
US20090143560A1 (en) 2009-06-04

Similar Documents

Publication Publication Date Title
CN101300286B (en) Optical device and achromatic lens
KR102365797B1 (en) Polycarbonate resin, production method therefor, and optical molded body
TWI428369B (en) Production method of polycarbonate
TWI761484B (en) Polycarbonate resin composition and optical lens using the same
KR102321239B1 (en) Polycarbonate and optical member including same
KR102255780B1 (en) Polycarbonate resin composition, and optical material and optical lens each manufactured using same
JP7176535B2 (en) POLYCARBONATE RESIN COMPOSITION, METHOD FOR MANUFACTURING SAME, AND OPTICAL LENS
CN101680967B (en) Lens and optical unit using the same
JP2007057916A (en) Optical lens
JP5688101B2 (en) Optical lens made of aromatic-aliphatic polycarbonate resin
TW202200670A (en) Polycarbonate resin, and optical lens and optical film using same
JP2010256621A (en) Optical lens comprising high-refractive index polycarbonate copolymer
WO2023100777A1 (en) Polycarbonate resin composition and optical lens using same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant